Week 6

Dr. Emad Alhseinat

CHEG324: Mass Transfer

Chapter 3

Diffusion in concentrated solutions

 Dilute vs. concentrated (solution)
• Any mass flux include both convection and diffusion (Maxwell, 1860).
• Diffusion causes convection.
– Dilute solution: convection caused by diffusion is small and can be neglected.
– Concentrated solution: both convection and diffusion have to be considered.
• Difference between Heat transfer and Mass transfer
– Heat conduction can occur without convection
– Diffusion and convection always occur together

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Evaporation of benzene. This process is dominated by diffusion in dilute
solutions, but it includes both diffusion and convection in concentrated solutions.
4
 Total mass Mass transported Mass transported
transported
= by diffusion by convection

n  c (v  v a )  c v a  j a  c v a
1 1 1 1 1 1

n1 n1  c1 v1
Convective reference velocity
 mass  ???
 (area)(time) 
Average solute velocity
 
w.r.t fixed coordinate
Local concentration
Convective reference velocity v a
How to choose its value ?
Our goal: choose va so that va is zero as frequently as possible!

n  j a  c va The mass transfer reduced to “diffusion” only.

1 1 1

va can be:

• the molar average velocity

• good for ideal gases where the molar concentration is constant
• the mass average velocity
• good for constant-density liquid
• the volume average velocity
• good for constant-density liquid and for ideal gas 5
7
REVIEW OF SOME CONCEPT

 The mole fraction for liquid and solid mixture, x A ,and for gaseous mixtures, y A, are the molar
concentration of species A divided by the molar density of the mixtures.
CA
x A  (liquids and solids)
C

CA
y A 
C (gases)
The sum of the mole fractions, by definition must equal 1;
x i 1
i
y i 1
i
by similar way, mass fraction of A in mixture is;
A
wA 

 REVIEW OF SOME CONCEPT
• Average molecular weight

𝑀𝑎 𝑣 = ∑𝑛 𝑦𝑖 𝑀𝑖
• Mass concentration of species A “density” (𝜌𝐴): mass of A per unit volume of the
mixture
𝑛

• Total mass concentration (or density): total mass of the mixture in a unit volume 𝜌 = ∑ 𝜌𝑖
𝑖=1
𝜌𝐴
• Mass fraction of A 𝜔𝐴 =
𝜌
 REVIEW OF CONCEPT
•Molar concentration of A (𝐶𝐴): moles of A per unit volume of the mixture
𝜌𝐴
𝐶𝐴 =
𝑀𝐴

𝑀𝐴 is the molecular weight of species A

•Total molar concentration: total moles of the mixture in a unit volume
𝑛
𝐶 = ∑ 𝐶𝑖
𝑖=1

pA V
For ideal gas mixtures, n A  [ from Ideal gas law PV = nRT]
RT
nA p
C A   A
V RT

where pA is the partial pressure of species A in the mixture. V is the volume of gas, T is the absolute temperature, and R is the universal ga
The total molar concentration or molar density of the mixture is given by
 REVIEW OF CONCEPT
Velocities
 In a multicomponent system the various species will normally move at different velocities;
and evaluation of velocity of mixture requires the averaging of the velocities of each species
present.

If  i is the velocity of species i with respect to stationary fixed coordinates, then mass-average velocity
for a multicomponent mixture defined in terms of mass concentration is,

  i i   i i
  i  i
  i 
i
 By similar way, molar-average velocity of the mixture  * is

C i V i
 *  i
C

 For most engineering problems, there will be title difference in  * and  and so the mass average
velocity, , will be used in all further discussions.

 The velocity of a particular species relative to the mass-average or molar average velocity is termed
as diffusion velocity

(i.e.) Diffusion velocity =  i - 

 Fluxes

 Flux is the amount of species that passes per unit time through a unit area normal to the flow direction
(vector)

• Mass flux of species i relative to fixed coordinates is:

• Total mass flux is:

• Molar flux of species i relative to fixed coordinates is:

• Total molar flux is:

DIFFUSION FLUX

Mass flux of species i

ji is the mass diffusion flux of species i relative to the

mass-average velocity

Molar flux of species i

Ji is the molar diffusion flux of species i relative to the molar-average

velocity
 The temperature and pressure are such that the
diffusion coefficient is 0.1 cm2/sec. The length l is
nitrogen hydrogen 10 cm. Find the molar average velocity v*, the mass
average velocity v, the volume average velocity v0
at the average concentration in the system.

The volume in this system does not move, so v0 = 0. If the gases are ideal, the
molar concentration is constant, so v* = 0.
D
j cv  (c  c ) Diffusion in the thin-film
1 1 1 10 1l
l
D c10  c1l 0.1 1 0
v1  ( ) ( )  0.02 cm / sec For nitrogen at an average
l c 10 0.5 concentration of 0.5 c
1
D c20  c2l 0.1 0 1
v  ( ) ( )  0.02 cm / sec For hydrogen at an average
2
l c2 10 0.5 concentration of 0.5 c
~
cM 0.5(28)
w1  c ~ 1 c1 ~  0.5(28)  0.5(2)  0.933 Mass fraction of nitrogen
1M 1 2M 2

c2 M 2 0.5(2)
w2    0.067 Mass fraction of hydrogen
c M c M 0.5(28)  0.5(2)
1 1 2 2
10
v  v1w1  v2w2  0.933(0.02)  0.067(0.02)  0.017 cm / sec
For gases (e.g. H2 and N2) at equal T and p the number of
moles is always the same in both sides. Similarly the
volume in both sides is the same. As a result, the
v0 = 0 volume average velocity

v* = 0 molar average velocity

v  0 mass average velocity,

because the masses of N2 and H2 are different. As a

result, as time goes by the center of mass in the two-
bulb apparatus moves away from the bulb containing N2
initially. Thus the mass average velocity v is not zero.

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For liquids: The volume is nearly always constant. v0 = 0
volume average velocity
v = 0 mass average velocity. This is usually correct as liquid
densities differ little.
e.g. H2O=1 g/cm3
Glycerol=1.1 g/cm3
However, the molar concentration is usually quite different
following large differences in molecular weight.
e.g. MWH2O=18 g/mol and
MWGlycerol=92 g/mol
So v*0 molar average velocity for liquids.
In conclusion: For gases use as reference velocity va the v0 or v*,
while for liquids use v0 or v.

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Parallel Diffusion and Convection

Example 3.2.1: Fast diffusion through a stagnant film

Goal: Calculate the flux and

the concentration profile

Remember that at intermediate

temperatures both diffusion
and convection affect the
evaporation of benzene (or any
other solute).

Now both diffusion and

convection are important!

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 z
Fast evaporation by
l diffusion and convection

z
A mass balance on a differential volume A z gives:

Solute Solute Solute

accumulated in = transported transported out
volume Az in at z at z + z


Azc1   An1 z  An1
t
zz

Dividing A z
z  0
c1 n1

t z 18
c1 n1 contribution of both diffusion and convection and it is constant.

t z
s.s choose volume average velocity v0

n  j a  c va
1 1 1

dc1
n1  D  c1 (c1V1v1  c2 V2 v2 )
dz
If the solvent vapor is stagnant or we have
n1  c1v1 just one component

dc1
n1  D  c1V1n1
dz
RT 1
V1   Total molar concentration
p c

dc1 c1 dy1
n1  D  n1 n1  Dc  y1n1
dz c dz 19
 dy1
n1  Dc  y1n1
dz dy1
j1  Dc
B.C. dz
y1  y10 z0
y1  y1l zl
n1  const.

1 y1  1 y1l 
z /l

 
1 y10  1 y10 
Exponential concentration profile
z /l
 1 y10  1 y1l   1 y1l 
Dc  1 y1l  j1  Dc   ln 
n1  ln  l   1 y10   1 y10 
l  1 y10  The diffusion flux is smallest at the bottom of the capillary
n1 = constant and rises to a maximum value at the top of the capillary.
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 1 y1  1 y1l  Dc  1 y1l 
z /l z/l

    1 y10  1 y1l  ln 1 y1l 

n1  ln  j1  Dc 
1 y10  1 y10 
 l  1 y10   l  1 y10   1 y10 

Concentrated solution

Dilute solution
z
1 y1  1 y10  ( y10  y1l )  ...
l
n1  j1 
Dc
y10  y1l   D c10  c1l 
l l
or

z
c1  c10  (c1l  c10 )
l

Linear concentration profile

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Concentration and flux in concentrated diffusion. The
concentration profile is no longer linear. The constant
total flux is the sum of diffusion and convection, each
of which varies. 22
 Taylor and Maclaurin Series

f "(c)
f (x)  f (c)  f '(c)(x  c)  (x  c) 2  ...
2!

If c = 0, the series is the

Maclaurin series for f

f(x) = (1 + x)k. This produces the binomial series.

k  (k 1)x 2 k  (k 1) ...(k  n 1)  x n

f (x)  (1 x)  1 k  
k
 ... 
2 n!

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Now does this result reduce to that for dilute
solutions?

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 How important is the convection term?
The vapor pressure of benzene at 6ºC is about 37 mmHg l
The vapor pressure of benzene at 60ºC is about 395 mmHg
z
c1 p1 (sat) 37
y1 6 ∘C
    0.049
c p 760
c p (sat) 395
y1  1 1   0.520
60∘C
c p 760

Total flux Dc  1 y1l  n1 

Dc
y10  y1l 
n1  ln l
l  1 y10 
Diffusion + convection Diffusion
Dc  1 0  n1 
Dc
0.049  0
6 ºC n1  ln   2%
l  1 0.049  l
Dc  1 0 
60 ºC n1  ln   n1 
Dc
0.52  0 40 %
l  1 0.52  l 28
Fast Diffusion into a Semiinfinite slab
In this problem, a volatile liquid solute evaporates into a long gas-filled capillary.
As solute evaporates, the interface between the vapor and the liquid solute drops.
A mass balance on a differential volume A z gives:

Solute Solute Solute

accumulated in = transported transported out
volume Az in at z at z + z


Azc1  An1 z  An1
t
zz

Dividing A z
z  0
c1 n1

Fast evaporation by diffusion
t z
and convection
59
c1 n1

t z choose volume average velocity v0

n  j a  c va
1 1 1

c1   c1 
   D  c1 (c1V1v1  c2 V2 v2 ) 
t z  z 
n1  c1v1 n 2  c2v2

c1  2 c1 c1 (n1V1  n2V2 )

D 2 
t z z independent of z
 =1 
(c V  c V   (n V  n V ) Continuity equation
2 2)
t z
1 1 1 1 2 2

c1  2 c1 c1
 D 2  (n1V1  n2V2 )
t z z 60
c1  2 c1 c1
 D 2  (n1V1  n2V2 )
t z z
n 2  0 Solvent gas is insoluble

c1  2 c1 c1
 D 2  (n1V1 z0 )
t z z
c1
n1  D z 0  c1V1n1
z
z0 z0

c1  2 c1 c1 c1

 D 2 V1 (D z0  c1V1n1 z0 )
t z z z

c1  2 c1 c c1
 D 2 V1 (D 1 z0  c1V1n1 z0 )
t z z z
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c1  2 c1 c1 c1 B.C.
 D 2 V1 (D z0  c1V1n1 z0 ) t  0, all z  0, c1  0
t z z z
t  0, z  0, c1  c1 (sat)
z
 t  0, z  , c1  0
4Dt
1 c1 
   V1(D z0  c1V1n1 z0 
)
2 z 
  0, c1  c1 (sat)
d 2 c1 dc1
 2(  ) 0   , c1  0
d 2
d

c1 1 erf (  )

c1 (sat) 1 erf

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General form of the mass balance equation
z Input rate through ABCD n x y  z
y C G Input rate through ADHE n y  x z
x D
H
Input rate through ABFE n z  x y

z B Output rate through EFGH nxyz  n xyz x
F x
y
n yxz  nyxzy

Output rate through BCGF
A x E y

Output rate through CDHG n zxy  n zxy z
z

input - output + generation = accumulation



nxyzx   nyxzy   n zxyz  r1 xyz  c xyz
x y z t



nx   n y   nz  r1  c
x y z t
 c
   n  r1 
t

n  j0  cv 0 Diffusion and the convection term

c
 D  2  c    cv 0  r1
t

General equation include the effects of chemical reaction, convection,

and concentration-driven diffusion
Combine with Fick’s law
c 
  nx 
n  n  r
 
t x y y z z 1

c 1 
 rnr  1  n   n z  r1
t r r r  z
c 1  2
t
 2
r r
 
r nr 
1 
r sin  
n sin   1 
r sin  
n  r1
64
Overall mass balance (continuity equation)
 Example 3.4-1: Fast diffusion through a stagnant film and into a semi-infinite slab

Find differential equations describing these two situations from the general equations in Tables 3.4-
1 to 3.4-3. Compare your results with the shell-balance results in the previous section.

Solution: This evaporation is

 steady state, has no chemical reaction, and
occurs only in the z direction.
 Thus Eq. A in Table 3.4-1 becomes

Alternatively, for constant density, Eq. A in Table 3.4-2 becomes

Either of these equations leads to a solution of the problem like that in shell-balance.
 Fast diffusion into a semi-infinite slab

 Unsteady
 The process is one-dimensional,
 No chemical reaction.
 From Eq. A in Table 3.4-1, we find

Alternatively, for constant density, Eq. A in Table 3.4-2 becomes

The first term on the left-hand side of this result represents accumulation and the second is convection. The
right-hand side represents diffusion.

Again, the solution to these equations parallels that in the previous section.
A Guide to Previous Work

 Diffusion in concentrated solutions is complicated by the convection caused by the diffusion process.

 This convection must be handled with a more complete form of Fick’s law, often
including a reference velocity

 The best reference velocity is the volume average, for it is most frequently zero.

 The results in this chapter are valid for both concentrated and dilute solutions; so
they are more complete than the limits of dilute solutions given in Chapter 2.

Advice from Prof Cussler “Think dilute.”